CN106328895A - Graphene-coated silkworm excrement hierarchical porous carbon-sulfur composite anode material and preparation method thereof - Google Patents
Graphene-coated silkworm excrement hierarchical porous carbon-sulfur composite anode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a graphene-coated silkworm excrement hierarchical porous carbon-sulfur composite anode material and a preparation method thereof. The preparation method includes: mixing silkworm excrement with ZnCl2, placing into a high-temperature tube furnace, and performing heating reaction under protective gas to obtain silkworm excrement hierarchical porous carbon SPCH; pouring into powdered sulfur, and allowing the powdered sulfur not to directly contact with the SPCH; vacuumizing, sealing, placing into a drying oven, and performing heating reaction to obtain an SPCH/S1 composite material; placing the SPCH/S1 composite material into a sodium thiosulfate solution, standing, dropwise adding a hydrochloric acid solution to perform chemical deposition secondary sulfur loading reaction for 2-5 hours, and drying after centrifugal filtration to obtain an SPCH/S composite material; coating the SPCH/S composite material with graphene oxide, and performing microwave irradiation reduction to obtain the graphene-coated silkworm excrement hierarchical porous carbon-sulfur composite anode material G-SPCH/S. The graphene-coated silkworm excrement hierarchical porous carbon-sulfur composite anode material and the preparation method thereof have the advantages that a vacuum-steam method and a chemical solution deposition method are used to perform sulfur loading, the absorption acting force and uniform dispersity of sulfur on a carrier can be evidently increased, and the cycle life of a battery can be prolonged by graphene coating.
Description
Technical field
The invention belongs to materials chemistry and technical field of electrochemistry, be specifically related to porous carbon material and lithium-sulfur cell material thereof
And preparation method thereof.
Background technology
Excessively exploitation and a large amount of consumption of fossil energy have caused increasingly serious global energy crisis and environmental problem, sternly
The living environment of the mankind and socioeconomic sustainable development are heavily threatened.Therefore, accelerate that particularly clean new forms of energy can be again
The development and utilization of the raw energy is human society in the top priority of the facing of new century and severe challenge.Circulation can use
Secondary cell is the excellent energy storage device of various regenerative resource (such as solar energy, wind energy, tide energy etc.), is that following cleaning can be again
The raw indispensable important composition of the energy, has great social need.
In recent years, lithium-sulfur cell receives much concern as the lithium secondary battery of a new generation's high-energy-density.Its theory compares energy
Amount may be up to 2600Wh/kg, exceeds 6-7 times than lithium ion battery energy density, sustainable kart continuation of the journey 500-
More than 800km, thus receive much concern, and be considered as one of the most promising energy-storage battery system in future.
In lithium-sulfur cell, the performance of sulfur positive electrode is the key determining lithium-sulfur cell quality height.But, it is limited to sulfur
And the electric conductivity that discharging product lithium sulfide is poor, and produce in the middle of a series of many lithium sulfides formed in charge and discharge process
Thing is soluble in the shortcomings such as organic electrolyte, and it is relatively low (particularly under high current density that lithium-sulfur cell still suffers from sulfur positive pole utilization rate
Discharge and recharge) and cycle performance difference etc. problem, become hinder the actual application of lithium-sulfur cell maximum bottleneck.
If can sulfur be homogeneously dispersed among the porous material that a kind of electric conductivity is good with small particle size form, a side
Face can be effectively improved the utilization rate of sulfur；On the other hand, the surface adsorption effect utilizing conductive carrier can effectively suppress again
Sulfur and the discharging product (many lithium sulfides) loss on anode pole piece thereof.Therefore, height can be prepared by compound to sulfur and material with carbon element
Capacity and the anode composite material of lithium sulfur battery of cycle performance excellence.Bombyx mori L. is the main garbage of Bombyxmori Linnaeus industry, at rural area warp
Chang Suiyi abandons and causes environmental pollution, understands it from Electron microscope observation and has natural three-dimensional drape structure and phosphorus content height,
High-ratio surface multiporous biological charcoal can be obtained through high temperature cabonization and activation.
At present, people's many employings one step melts diffusion method and the injection of sulfur component is carried formation lithium sulfur positive pole composite wood in sulfur materials
Material.There is following problem in this method: (1) sulfur is the best with the wellability of porous material hole wall in the molten state, it tends to be difficult to
Go deep into inside duct particularly in micropore hole, and block duct；(2) sulfur component is relatively low with porous material hole wall adhesion, dispersion
Uneven.These two aspects have impact on the high rate performance that composite is overall to a great extent, is easily caused composite simultaneously
Middle utilization efficiency is the highest, and the discharge capacity of battery reduces；In addition sulfur component is difficult to diffuse into micropore canals, reduces it and carries sulfur
The adsorption of material, the polysulfide causing reaction to generate is easier to be dissolved in organic electrolyte, accelerates lithium-sulfur cell
Capacity attenuation speed.
Summary of the invention
The present invention is directed to existing porous material carry that sulfur is uneven and absorption affinity is weak and cause composite cycle performance difference etc.
Problem, it is provided that a kind of graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole and preparation method thereof, utilizes gas phase steam to inhale
Sulfur component is supported in the duct of Bombyx mori L. multi-stage porous charcoal by the process of attached-chemical solution deposition with nano particle size, then by molten
Liquid method cladding graphene oxide sheet, then by microwave irradiation, graphene oxide sheet is reduced into Graphene, it is thus achieved that long-life
Carbon sulfur composite positive pole.
The purpose of the present invention is achieved through the following technical solutions:
A kind of graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole, the porous carrier of this material have mesopore (2～
50nm) and two kinds of ducts of micropore (< 2nm), its micropore has a strong adsorption to sulfur molecule, and mesopore be electronics, ion with
And the discharging product of sulfur and sulfur provides quick diffusion admittance；The BET specific surface area of obtained SPCH material is at 1200m2/ g with
On, micropore average pore size existsThe average pore size of mesopore existsAfter graphene film is coated with, following of material
Ring performance has had and has been obviously improved.Obtained SPCH/S composite is up to more than 1000mAh/g at 1.0C discharge capacity, and
Circulating the specific discharge capacity after 200 circles under 1.0C and be up to more than 800mAh/g, capability retention is up to more than 90%.
The preparation method of the graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole of the present invention, comprises the steps,
(1) preparation of Bombyx mori L. multi-stage porous charcoal: by Bombyx mori L. and ZnCl2Powder mixes, and is placed in high temperature process furnances, logical protection gas
After body purging, it is heated to 300-700 DEG C and carries out reaction and obtain Bombyx mori L. multi-stage porous charcoal；It is designated as SPCH；
(2) Bombyx mori L. multi-stage porous charcoal uploads sulfur: first put in quartz ampoule by Bombyx mori L. multi-stage porous carbon powder, then pours sulfur powder into and enter stone
Ying Guanzhong, does not directly contact with Bombyx mori L. multi-stage porous charcoal；Put into drying baker after evacuation, sealing, be warming up to 120～160 DEG C, then
Constant temperature takes out after keeping 8～20h and naturally cools to room temperature, obtains SPCH/S1Composite；
(3) secondary carries sulfur: by SPCH/S1Composite is placed in hypo solution standing, then drips hydrochloric acid solution
Carry out chemical deposition secondary and carry reaction of Salmon-Saxl 2～5h, after centrifugal filtration, obtain graphene coated Bombyx mori L. multi-stage porous charcoal sulfur in drying multiple
Close positive electrode, be designated as SPCH/S composite.
(4) graphene coated process: SPCH/S composite is placed in the aqueous solution of graphene oxide, SPCH/S and oxygen
Sample, after 5-19:1, stirring certain time, is taken out and is placed in microwave reactor heating by the mass ratio of functionalized graphene, microwave
Reaction temperature controls at 100-150 DEG C, and the response time is 5-15min, obtains graphene coated Bombyx mori L. multi-stage porous charcoal sulfur compound just
Pole material G-SPCH/S.
Further preferred as scheme, in described step (1), the high temperature cabonization response time is 0.5～5h, protectiveness gas
Body can use the noble gases such as nitrogen, argon；ZnCl2It is (1～6) with the mass ratio of Bombyx mori L.: 1.
Further preferred as scheme, controls vacuum≤100Pa in quartz ampoule in described step (2)., drying baker is adopted
With can temperature programmed control drying baker, concrete temperature control process:
(a) temperature-rise period: rise to 120～160 DEG C from room temperature with the heating rate of 0.5～2.0 DEG C/min；
(b) thermostatic process: be placed in 120～160 DEG C and keep 10～15h；
(c) temperature-fall period: thermostatic process takes out after terminating immediately in drying baker, naturally cools to room temperature.
Further preferred as scheme, hypo solution and SPCH/S in described step (3)1The matter of composite
Amount ratio is 4～10:1, and time of repose is 5～10h.
Further preferred as scheme, in described step (3), hydrochloric acid is 3～11:1 with the mol ratio of sodium thiosulfate,
The concentration that can use sodium thiosulfate is 0.03～0.20mol/L, and concentration of hydrochloric acid is 3～10wt%.
Further preferred as scheme, in described step (4), the reaction temperature of microwave controls at 100-150 DEG C, reaction
Time is 5-15min.
The principle of the present invention: make gaseous sulfur Molecular Adsorption Bombyx mori L. multistage by vapor sorption mode the most under vacuum conditions
On the strongest adsorption site of hole Carbon Materials, the micropore canals of Bombyx mori L. multi-stage porous charcoal is formed sulfur microcrystals, obtains Bombyx mori L. multistage
Hole charcoal sulfur SPCH/S1Composite.Recycling chemical solution deposition is by SPCH/S1Composite is placed in Na2S2O3In solution, slow
Slowly drip hydrochloric acid solution, make sulfur slowly separate out on Bombyx mori L. multi-stage porous charcoal existing sulfur nucleus, form sulfur Load Balanced and absorption
The Bombyx mori L. multi-stage porous charcoal sulfur composite that power is strong, then outer layer is wrapped up in deposited Graphene, the outflow of sulfur component can be significantly inhibited, thus promote
The high rate capability of composite and long-acting cycle performance.
The graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole of the present invention circulates the electric discharge after 220 circles under 1.0C
Specific capacity is up to 850-890mAh/g, and capability retention is up to more than 90%, hence it is evident that carry sulfur gained higher than directly melted diffusion
Uncoated charcoal sulfur composite positive pole, is also 2～3 times of conventional lithium-ion battery material specific capacity.
Compared with prior art, the present invention is advantageous in that:
(1) carrier used in the present invention is Bombyx mori L. multi-stage porous charcoal, belongs to twice laid, wide material sources and with low cost,
Reaming one-step method completes, and process is simple and environmental protection.
(2) structure utilizing the fold that Bombyx mori L. itself has is carbon source, can form three-dimensional network intercommunication by reaming many
Level pore structure, micropore surface is conducive to improving the absorption affinity to sulfur, and mesopore then can provide conveying logical for lithium ion and electrolyte
Road, reduces lithium ion and the diffusional resistance of electrolyte.
(3) present invention uses vapor diffusion active sulfur component to be carried on equably in the duct of SPCH, can make
Sulfur component occupies the strongest adsorption site and forms little S crystal seed, more just can be supported on by force by more S by chemical solution deposition
Adsorption potential, this one side can be effectively improved the contact area of sulfur component and the adhesive force of carrier and sulfur component and conduction hole wall,
On the other hand also can be prevented effectively from melted diffusion method brings duct blocking linear, and then improves the utilization ratio of sulfur, energy simultaneously
Obtain the cycle performance of long-acting circulation.
(4) the graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole of the present invention, the Graphene shell energy of its outer layer
Effectively stop the excessive of sulfur component, make battery have higher high rate performance and excellent cycle performance, present good work
Industry application prospect.
(5) preparation method of the present invention is simple to operation, is suitable for large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is the SEM of Bombyx mori L.；
Fig. 2 is the SEM figure of Bombyx mori L. multi-stage porous charcoal；
Fig. 3 is the SEM figure of graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole embodiment 1；
Fig. 4 is the thermal gravimetric analysis curve figure of the embodiment of the present invention 1 and SPC/S composite；
After Fig. 5 embodiment of the present invention 1 activates 2 circles under 0.5C (840mA/g), the circulation under 1.0C (1680mA/g) multiplying power
Performance map.
Detailed description of the invention
The present invention will be further described with embodiment below in conjunction with the accompanying drawings, but the scope of protection of present invention is not
It is confined to the scope of embodiment statement.
Embodiment 1
The preparation method of a kind of graphene coated Bombyx mori L. multi-stage porous sulfur composite positive pole, comprises the steps,
(1) preparation of Bombyx mori L. multi-stage porous
At N2By 10.0g Faeces bombycis and 10.0g ZnCl in atmosphere2Powder is raised to 700 DEG C with the heating rate of 2 DEG C/min,
And cool to room temperature after keeping 0.5h at 700 DEG C, obtain Bombyx mori L. multi-stage porous charcoal, be designated as SPCH.
(2) vacuum-steam method uploads sulfur at Bombyx mori L. multi-stage porous
First 0.3g SPCH powder is laid in Noah's ark, and Noah's ark is slowly pushed the middle part of quartz ampoule.1g sulfur powder is fallen
Enter in quartz ampoule, directly do not contact with carbonization SPCH；Putting it into after evacuation (vacuum is at≤100Pa), sealing can program
In the drying baker of temperature control, being warming up to 120 DEG C according to the heating rate of 0.5 DEG C/min, constant temperature takes out natural cooling after keeping 20h
To room temperature, obtain SPCH/S1Composite.
(3) chemical solution deposition is at SPCH/S1On composite, secondary carries sulfur
By 0.1g SPCM/S1Composite is placed in the hypo solution of 100mL standing 5h, sodium thiosulfate
Concentration is at 0.03mol/L；Then the hydrochloric acid solution 12mL being slowly added dropwise concentration 3wt% fully reacts 2h；After centrifugal filtration, 80
Dry for standby at DEG C, sample is labeled as SPCH/S composite.
(4) graphene coated process: be placed in by 0.57g SPCH/S composite containing 100mg graphene oxide is water-soluble
In liquid, after stirring certain 2h time, being taken out by sample and be placed in microwave reactor heating, the reaction temperature of microwave controls 100
DEG C, the response time is 15min, obtains the SPCH/S composite sulfur positive electrode of graphene coated.
Embodiment 2
The preparation method of a kind of graphene coated Bombyx mori L. multi-stage porous sulfur composite positive pole, comprises the steps,
(1) preparation of Bombyx mori L. multi-stage porous
At N2By 10.0g Faeces bombycis and 30.0g ZnCl in atmosphere2Powder is raised to 700 DEG C with the heating rate of 5 DEG C/min,
And cool to room temperature after keeping 1.0h at 700 DEG C, obtain Bombyx mori L. multi-stage porous, be designated as SPCH.
(2) vacuum-steam method uploads sulfur at Bombyx mori L. multi-stage porous
First 1.0g Bombyx mori L. multi-stage porous SPCH powder is laid in Noah's ark, and Noah's ark is slowly pushed the middle part of quartz ampoule.
The sulfur powder of 2g is poured in quartz ampoule, does not directly contact with Bombyx mori L. multi-stage porous charcoal SPCH；Evacuation (vacuum is at≤100Pa),
Put it into after sealing and the drying baker of temperature programmed control can be warming up to 140 DEG C according to the heating rate of 1.0 DEG C/min, constant temperature
Take out after keeping 10h and naturally cool to room temperature, obtain SPCH/S1Composite.
(3) chemical solution deposition is at SPCH/S1On composite, secondary carries sulfur
By 0.6g SPCH/S1Composite is placed in the hypo solution of 200mL standing 7h, sodium thiosulfate
Concentration is at 0.12mol/L；Then the hydrochloric acid solution 120mL being slowly added dropwise concentration 6wt% fully reacts 4h；After centrifugal filtration,
Dry for standby at 80 DEG C, sample is labeled as SPCH/S composite.
(4) graphene coated process: be placed in by 1.0g SPCH/S composite containing 100mg graphene oxide is water-soluble
In liquid, after stirring certain 3h time, being taken out by sample and be placed in microwave reactor heating, the reaction temperature of microwave controls 110
DEG C, the response time is 12min, obtains the SPCH/S composite sulfur positive electrode of graphene coated.
Embodiment 3
The preparation method of a kind of graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole, comprises the steps,
(1) preparation of micropore Bombyx mori L.
At N2By 10.0g Faeces bombycis and 40.0g ZnCl in atmosphere2Powder is raised to 600 DEG C with the heating rate of 3 DEG C/min,
And cool to room temperature after keeping 2.0h at 600 DEG C, obtain Bombyx mori L. multi-stage porous charcoal, be designated as SPCH.
(2) vacuum-steam method uploads sulfur at Bombyx mori L. multi-stage porous charcoal
First 2.0g Bombyx mori L. multi-stage porous charcoal SPCH powder is laid in Noah's ark, and Noah's ark is slowly pushed in quartz ampoule
Portion.A certain amount of sulfur powder is poured in quartz ampoule, does not directly contact with Bombyx mori L. multi-stage porous charcoal SPCH；Evacuation (vacuum≤
100Pa), put it into after sealing and the drying baker of temperature programmed control can be warming up to 160 according to the heating rate of 2.0 DEG C/min
DEG C, constant temperature takes out after keeping 8h and naturally cools to room temperature, obtains SPCH/S1Composite.
(3) chemical solution deposition is at SPCH/S1On composite, secondary carries sulfur
By 1.0g SPCH/S1Composite is placed in the hypo solution of 300mL standing 10h, sodium thiosulfate
Concentration is at 0.20M；Then the hydrochloric acid solution 240mL being slowly added dropwise concentration 10wt% fully reacts 5h；After centrifugal filtration, at 80 DEG C
Lower dry for standby, sample is labeled as SPCH/S composite.
(4) graphene coated process: be placed in by 1.8g SPCH/S composite containing 100mg graphene oxide is water-soluble
In liquid, after stirring certain 1h time, being taken out by sample and be placed in microwave reactor heating, the reaction temperature of microwave controls 150
DEG C, the response time is 5min, obtains the SPCH/S composite sulfur positive electrode of graphene coated.
Embodiment 4
The preparation method of a kind of graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole, comprises the steps,
(1) preparation of Bombyx mori L. multi-stage porous charcoal SPCH
At N2By 10.0g Faeces bombycis and 50.0g ZnCl in atmosphere2Powder is raised to 500 DEG C with the heating rate of 6 DEG C/min,
And cool to room temperature after keeping 3.0h at 500 DEG C, obtain Bombyx mori L. multi-stage porous charcoal SPCH.
(2) vacuum-steam method uploads sulfur at Bombyx mori L. multi-stage porous charcoal
First 0.6g Bombyx mori L. multi-stage porous charcoal SPCH end is laid in Noah's ark, and Noah's ark is slowly pushed the middle part of quartz ampoule.
A certain amount of sulfur powder is poured in quartz ampoule, does not directly contact with Bombyx mori L. multi-stage porous charcoal SPCH；Evacuation (vacuum≤
100Pa), put it into after sealing and the drying baker of temperature programmed control can be warming up to 130 according to the heating rate of 1.0 DEG C/min
DEG C, constant temperature takes out after keeping 15h and naturally cools to room temperature, obtains SPCH/S1Composite.
(3) chemical solution deposition is at SPCH/S1On composite, secondary carries sulfur
By 0.3g SPCH/S1Composite is placed in the hypo solution of 150mL standing 6h, sodium thiosulfate
Concentration is at 0.07M；Then the hydrochloric acid solution 60mL being slowly added dropwise concentration 4wt% fully reacts 3h；After centrifugal filtration, at 80 DEG C
Dry for standby, sample is labeled as SPCH/S composite.
(4) graphene coated process: be placed in by 1.8g SPCH/S composite containing 100mg graphene oxide is water-soluble
In liquid, after stirring certain 1h time, being taken out by sample and be placed in microwave reactor heating, the reaction temperature of microwave controls 130
DEG C, the response time is 10min, obtains the SPCH/S composite sulfur positive electrode of graphene coated.
Embodiment 5
The preparation method of a kind of graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole, comprises the steps,
(1) preparation of Bombyx mori L. multi-stage porous charcoal SPCH
At N2By 10.0g Faeces bombycis and 60.0g ZnCl in atmosphere2Powder is raised to 300 DEG C with the heating rate of 4 DEG C/min,
And cool to room temperature after keeping 5.0h at 300 DEG C, obtain Bombyx mori L. multi-stage porous charcoal SPCH.
(2) vacuum-steam method uploads sulfur at Bombyx mori L. multi-stage porous charcoal SPCH
First 1.5g Bombyx mori L. multi-stage porous charcoal SPCH powder is laid in Noah's ark, and Noah's ark is slowly pushed in quartz ampoule
Portion.A certain amount of sulfur powder is poured in quartz ampoule, does not directly contact with Bombyx mori L. multi-stage porous charcoal SPCH；Evacuation (vacuum≤
100Pa), put it into after sealing and the drying baker of temperature programmed control can be warming up to 150 according to the heating rate of 2.0 DEG C/min
DEG C, constant temperature takes out after keeping 13h and naturally cools to room temperature, obtains SPCH/S1Composite.
(3) chemical solution deposition is at SPCH/S1On composite, secondary carries sulfur
By 0.8g SPCH/S1Composite is placed in the hypo solution of 250mL standing 9h, sodium thiosulfate
Concentration is at 0.18M；Then the hydrochloric acid solution 190mL being slowly added dropwise concentration 9wt% fully reacts 4h；After centrifugal filtration, at 80 DEG C
Lower dry for standby, sample is labeled as SPCH/S composite.
(4) graphene coated process: be placed in by 1.9g SPCH/S composite containing 100mg graphene oxide is water-soluble
In liquid, after stirring certain 3h time, being taken out by sample and be placed in microwave reactor heating, the reaction temperature of microwave controls 120
DEG C, the response time is 5min, obtains the SPCH/S composite sulfur positive electrode of graphene coated.
Material properties test:
(1) surface topography of G-SPCH/S composite
Embodiment 1, Bombyx mori L. multi-stage porous charcoal and the Bombyx mori L. the present invention prepared carry out electron-microscope scanning, obtain Fig. 1's～Fig. 3
SEM schemes.
Fig. 1 is the SEM photograph of Faeces bombycis, and Fig. 2 is the SEM photograph of Bombyx mori L. multi-stage porous charcoal SPCH, and Fig. 3 is that the present invention prepares
The SEM photograph of embodiment 1.
Comparison diagram 1 with in Fig. 2 it can be seen that compared with Faeces bombycis, Bombyx mori L. multi-stage porous charcoal wrinkled surface fades away, occur
Very abundant duct and channel design, channel interior is also may be seen indistinctly the most tiny duct, presents multiple pore
Road net distribution general layout.This structure is advantageous to the load of S.Fig. 3 surface is substantially coated with one layer of lamellar material, is stone
Produced structure after ink alkene cladding.
(2) Bombyx mori L. multi-stage porous charcoal, SPC/S1And the pore structure parameter of SPC/S composite
Use the ASAP-2020 specific surface pore-size distribution instrument that Micro company of the U.S. produces to Bombyx mori L. multi-stage porous SPC, SPC/
S1And the pore structure of SPC/S composite characterizes, result is as shown in table 1.
Table 1 Bombyx mori L. multi-stage porous charcoal, the pore structure parameter of SPCM/S and G-SPCM/S
As can be seen from Table 1, Bombyx mori L. multi-stage porous charcoal SPCH has higher specific surface area, and itself Langmuir and BET compares table
Area is respectively 955 and 1202m2/ g, total pore volume is 0.42cm3/g.This illustrates after high-temperature activation reacts, Faeces bombycis duct
Interior oxy radical and some tar components are removed, activator ZnCl simultaneously2There is strong taking hydrogen by force and take oxygen function by force, by silkworm
The multi-stage porous pore passage structure of micropore and mesopore is etched on husky internal channel.This material is that one has multi-stage porous (in/micropore) carbon
Material, wherein micropore can form stronger adsorption to sulfur and polysulfide, is favorably improved following of sulfur composite
Ring stability；Hollow sections then can provide transfer passage for lithium ion and electrolyte, reduces lithium ion and the expansion of electrolyte
Dissipate resistance, improve the high rate performance of battery.
After carrying sulfur by steaming process and further chemical solution deposition, the specific surface area of SPCH/S significantly declines,
Langmuir specific surface area only remains 199m2/g；Its pore volume the most significantly declines, the 26% of only SPCH pore volume；Additionally, micropore hole
Holding and micropore specific area the most significantly declines, this surface sulfur component (connects granule from the exit orifice of Bombyx mori L. multi-stage porous charcoal
The macropore or mesoporous on surface) it is diffused among endoporus.
(3) thermogravimetric curve of G-SPCH/S composite
The STA449C structural synthesis thermal analyzer using NETZSCH company of Germany to produce is multiple to the SPC/S prepared by the present invention
Condensation material carries out heat stability testing, and test condition is: nitrogen protect, heating rate is 10 DEG C/min, temperature elevating range be 100～
420℃.Test result is as shown in Figure 3.
From fig. 4, it can be seen that embodiment 1 prepared by the present invention starts weightlessness to occur, to weight when 362 DEG C at 265 DEG C
No longer changing, weightlessness terminates, and its weight-loss ratio is about 62.0%.Weight-loss ratio corresponds to the sulfur content of composite, and i.e. this is answered
The sulfur content of condensation material is about 62.0%.Contrast material SCPH/S, the temperature that sulfur overflows after graphene coated has raised.
As can be seen here, preparation method of the present invention is conducive to obtaining the composite positive pole of high sulfur content, the evaporation temperature of S simultaneously
Spend higher explanation S stronger with the adsorption of Bombyx mori L. multi-stage porous charcoal.
(4) chemical property of G-SPCH/S composite
After Fig. 5 shows that the embodiment of the present invention one G-SPCH/S composite activates 4 circles under 0.2C (334mA/g),
Cycle performance figure under 1.0C (1680mA/g) multiplying power.As it can be seen, after material circulates 200 circles under 1.0C, its specific volume that discharges
Amount is still up to 837mAh/g, and its capability retention is up to 90.5%.This explanation, G-SPCH/S composite is in the condition tested
Being respectively provided with higher coulombic efficiency, this also illustrates that S is more tight with the combination of carrier Bombyx mori L. multi-stage porous charcoal, Bombyx mori L. multi-stage porous simultaneously
Charcoal also shows the most excellent electric conductivity.
Table 2 showing, the electric discharge under different multiplying of the five kinds of embodiment gained G-SPCH/S composites of the present invention is held
Amount.As seen from the table, the G-SPCH/S composite high rate performance obtained by scope of experiment involved in the present invention is the most relatively
For excellence.Battery specific discharge capacity under 3.0 and 6.0C is up to 821-873 and 665-725mAh/g respectively；As can be seen here, material
Material cyclo-stationary of material in tested multiplying power change procedure, has higher specific discharge capacity under high magnification.This with
The big passage of sulfur-donor Bombyx mori L. multi-stage porous charcoal is relevant with the quickly conduction of electronics to lithium ion, and the outer Graphene wrapped up in promotes in addition
The electric conductivity that positive electrode is overall, and then improve the high rate performance of material.
The 2 five kinds of embodiment gained G-SPCH/S composites of table discharge capacity under different multiplying
Claims (10)
1. a graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole, it is characterised in that: this material discharges under 1.0C
Capacity is up to more than 1000mAh/g, and circulates the specific discharge capacity after 200 circles under 1.0C and be up to more than 800mAh/g, capacity
Conservation rate is up to more than 90%.
2. the preparation method of graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole as claimed in claim 1, its feature
It is: comprise the steps,
(1) preparation of Bombyx mori L. multi-stage porous charcoal: by Bombyx mori L. and ZnCl2Powder mixes, and is placed in high temperature process furnances, and logical protective gas blows
After sweeping, reacting by heating obtains Bombyx mori L. multi-stage porous charcoal SPCH；
(2) Bombyx mori L. multi-stage porous charcoal uploads sulfur: first put in quartz ampoule by Bombyx mori L. multi-stage porous charcoal, then pours sulfur powder into and enter in quartz ampoule,
Directly do not contact with Bombyx mori L. multi-stage porous charcoal；Putting into drying baker after evacuation, sealing, be warming up to 120～160 DEG C, then constant temperature is protected
Take out after holding 8～20h and naturally cool to room temperature, obtain SPCH/S1Composite；
(3) secondary carries sulfur: by SPCH/S1Composite is placed in hypo solution standing, then drips hydrochloric acid solution
Learn deposition secondary and carry reaction of Salmon-Saxl 2～5h, after centrifugal filtration, obtain Bombyx mori L. multi-stage porous composite sulfur positive electrode in drying；
(4) graphene coated process: SPCH/S composite is placed in the aqueous solution of graphene oxide, SPCH/S and oxidation stone
The mass ratio of ink alkene, after 5-19:1, stirring mixing, is placed in reacting by heating in microwave reactor, obtains graphene coated Bombyx mori L. many
Level hole charcoal sulfur composite positive pole G-SPCH/S.
The preparation method of graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole the most according to claim 2, it is special
Levying and be: in described step (1), reacting by heating temperature is 300-700 DEG C, the time is 0.5～5 hour.
The preparation method of graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole the most according to claim 2, it is special
Levy and be: ZnCl in described step (1)2It is 1～6:1 with the mass ratio of Bombyx mori L..
The preparation method of graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole the most according to claim 2, it is special
Levy and be: vacuum≤100Pa in quartz ampoule in described step (2).
The preparation method of graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole the most according to claim 2, it is special
Levy and be: in described step (2) drying baker use can temperature programmed control drying baker, concrete temperature control process:
(a) temperature-rise period: rise to 120～160 DEG C from room temperature with the heating rate of 0.5～2.0 DEG C/min；
(b) thermostatic process: be placed in 120～160 DEG C and keep 10～15h；
(c) temperature-fall period: thermostatic process takes out after terminating immediately in drying baker, naturally cools to room temperature.
The preparation method of graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole the most according to claim 2, it is special
Levy and be: hypo solution and SPC/S in described step (3)1The mass ratio of composite is 4～10:1.
8. according to the preparation method of the graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole described in claim 2 or 5, its
It is characterised by: in described step (3), hydrochloric acid is 3～11:1 with the mol ratio of sodium thiosulfate.
The preparation method of graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole the most according to claim 2, it is special
Levy and be: in described step (3), the concentration of sodium thiosulfate is 0.03～0.20mol/L；In described step (3), concentration of hydrochloric acid is
3～10wt%.
The preparation method of graphene coated Bombyx mori L. multi-stage porous charcoal sulfur composite positive pole the most according to claim 2, it is special
Levying and be: in described step (4), the reaction temperature of microwave controls at 100-150 DEG C, the response time is 5-15min.
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